Dyestuffs containing metals and process of making same



Patented Nov. 25 1930 UNITED, STATES PATENT OFFICE HANS G'UBLER, OF BASEL, SWITZERLAND, ASSIGNOR TO THE FIRM SOCIETY OF CHEMI- CAL INDUSTRY IN BASLE, 0F BASEL, SWITZERLAND DYES'IUFFS CONTAINTNG METALS AND PROCESS OF MAKING SAME No Drawing. Application filed July 9, 1929, Serial No. 377,069, and in Switzerland July 14, 1928.

The present invention relates to new dyestuffs containing metals. It comprises the new products, the method of producing same in substance, in the dye-bath, or on the fiber, the application thereof and the material which has been dyed with the new products.

It has been found that the new dyestuffs containing complex bound metals which correspond to azo-dyest1ifis of the general formula wherein m stands for an organic residue contalnlng at least one carbon atom, the

groups being linked to such carbon atoms of said residue which are united by a double bond with a nitrogen, oxygen or sulfur atom, and wherein R means the residue of a benzene nucleus characterized by the presence of a COOK-group (R=H or alkyl) standing in ortho-position to the N=N group, R is an aryl nucleus, and R, an aryl nucleus which carries a carboxyl group and a OH- group standing in ortho-position to each other, are very valuable cotton dyestuffs which yield on the vegetable fiber, as well as on artificial fibers of the group of the regenerated cellulose, such as viscose or cuprammonium silk tints, particularly orange to brown, red, Bordeaux and brown, which may be distinguished by an excellent fastness to light.

As metals which are capable of forming complex compounds come first of all into question: copper, cobalt, nickel; further aluminium, vanadium, chromium, titanium, manganese, iron, molybdenum, cerium, uramum.

These dyestufis are most conveniently obtained by combining intermediate products of the general formula wherein 50, R and R have the same meaning as above stated, with diazo-compounds containing in ortho-position to the N=N group a COOH- or COO-alkyl group; such products are for example the anthranilic acids, the anthranilic acid esters, the sulfoanthranilic acids, the nitroor chloro-anthranilic acids, the 2-aminonaphthalene-3-carboxylic acids, and the like. The disazo-dyestuffs thus obtained are then treated with agents yielding copper, chromium, manganese, etc., which operation may be perforn'ied in substance, in the dye-bath or on the fiber.

The same dyestuffs may be obtained by uniting 1 molecular proportion of an azodyestuif of thegeneral formula in which R, has the same meaning as above stated, and 1 molecular proportion of an azodyestuif of thegeneral formula wherein R and B, have the same meaning as above stated, with compounds corresponding to the residue :0 already described hereinbefore, i. e. inter alia phosgene, carbon disulfide, thiophosgene, triazine compounds having at least 2 halogen atoms capable of reacting, quinazolines or pyridazines halogenated at least twice in the heterocyclic nucleus, trichloropyrimidines, chloromethylpyrimidines, and the like.

The disazo-dyestuifs thus obtained are then treated with metallizing agents, such as salts,

oxides or h ;;droxides of the metals above named.

It is also possible to metallize the single azo- (.yestuii's separately and then combine same by 1 cans of compounds which correspond to the residue as.

The following examples illustrate the invention, the parts being by weight ExampZe J 52.7 parts of the unsymmetrical urea of one molecular pr portion of 2-amino-5-hydroxynaphthalene-T-sulfonic acid and one molecular proportion of 4-amino-azobenzenei-hydroxy-i-carboxyiic acid are suspended in the form of the sodium salt in 400 parts of water and the suspension is stirred with l l parts of caustic soda solution of 3 per cent. strength and 20 parts of calcined sodium carbonate. lVhile stirring at l012 C. the diazo-solution from 21.6 parts of 1- aminol-sulfobenzene-Q-carboxylic acid is added and when coupling is complete the dyestuff is isolated in the usual manner. It dyes cotton orange tints, which by after-treatment with copper salts, change towards brown, with chromium and-manganese salts slightly towards brown-red, with iron salts towards dark brown, with nickel salts towards light brown and with cobalt salts towards olivetinged brown.

The manufacture of one of these compounds, for instance the copper compound, is conducted as follows :The isolated dyestuif obtained according to the foregoing paragraph is stirred at -12 C. The diazosolution from 21.6 parts of 1-amino-tsulfobenzene-2-carboxylic acid is then added. When coupling is complete it is stirred in 1500 parts of water, heated to 60 C., acidified with dilute sulfuric acid and mixed with 60 parts of crystallized copper sulfate in the form of a solution of per cent. strength; the whole is stirred for 2-3 hours at EEO-85 C. and the copper compound, which has completely separated, is filtered. The dyestuff acid is stirred with dilute sodium carbonate solution and the sodium salt thus produced is salted out by means of common salt. The dyestui'f dyes cotton yellow-brown tints of excellent fastness to light.

Example 6 66.4 parts of the tertiary condensation product from 1 mol cular proportion of cyanuric chloride, 1 molecular proportion of 2- amino 5 hydroxynaphthalene 7 sulfonic acid, 1 molecular proportion of 4c-amino-azobenzene-4-hydroxy-3carboxylic acid and 1 molecular proportion of aniline are suspended, with addition of parts of sodium carbonate, in 600 parts of water, whereupon the whole is mixed with 14 parts of caustic soda solution of 30 per cent. strength and 20 parts of sodium carbonate. lVhile stirring at 10- 12 C. the diazo-solution from 21.6 parts of l-amino-4:-sulfobenzene-Q-carboxylic acid is added and when coupling is complete the dyestuif is isolated in the usual manner; it is stirred in 1500 parts of water, heated to 0., acidified with dilute sulfuric acid and mixed with 60 parts of crystallized copper sulfate in the form of a solution of 20 per cent. strength; the whole is stirred for 23 hours at -85 C. and the copper compound which has completely separated, is filtered. The dyestuffi acid is stirred with dilute sodium carbonate solution and the sodium salt thus produced is salted out by means of common salt. The dyestuif dyes cotton yellowbrown tints of excellent fastness to light.

A similar dyestufi' is obtained from the secondary condensation product derived from 1 molecular proportion of cyanuric chloride, 1 molecul; proportion of Q-amino-5-hydroxynaphthalene-T-sulfonic acid and 1 molecular proportion of 4 amino azobenzene i hydroxy-S-carboxylic acid.

Instead ofa-amino-azobenzene-4c hydroxy- 3-carboxylic acid similar mono-azo-dyestuifs can be used, such for example as 3-aminoazobenzene-a-l1ydroxy3-carboxylic acid, 4 amino-azobenzene-3-methylA-hydroxy-3-carboxylic acid, and the corresponding dyestuffs which derive from the ortho-cresotinic acid or the 1:2- or 2:3-hydroxynaphthoic acids.

What I claim is 1. As new articles of manufacture the azodyestuffs containing complex bound. metals which, on the one hand, correspond to the azodyestuffs of the general formula wherein :0 stands for an organic residue containing at least one carbon atom, the

groups being linked to such carbon atoms of said residue which are united by a double bond with a nitrogen, oxygen or sulfur atom, and wherein R means the residue of a henzene nucleus characterized by the presence of a COOK-group (R=H or allzyl) standing in ortho-position to the N=N group, R is an aryl nucleus, and R, an aryl. nucleus which carries a carboxyl group and a OH-group standing in ortho-position to each other, and which, on the other hand, contain complex bound metals of the atomic weight ranging between 52.1 and 63.6, which products form dark powders dyeing the vegetable fiber yellow-brown to orange reddish-brown tints.

2. As new articles of manufacture the azo dyestuffs containing complex bound copper corresponding to the azo-dyestuifs of the general formula I OH wherein m stands for an organic residue containing at least one carbon atom, the

groups being linked to such carbon atoms of said residue which are united by a double bond with a nitrogen, oxygen or sulfur atom, and wherein R means the residue of a hen zene nucleus characterized by the presence of a COOR-group (R=H or alkyl) standing in ortho-position to the N=N- group, R is an aryl nucleus, and R an aryl nucleus which carries a carboxyl group and a OH-group standing in ortho-position to each other, which products form dark powders dyeing the vegetable fiber yellow-brown to orange reddish-brown tints.

As new articles of manufacture the amdyestuffs containing complex bound copper which correspond to the azo-dyestufis of the general formula wherein it stands for an organic residue containing at least one carbon atom, the

eral formula -N=NQOH COOH w 11 y f1 wherein 11 means 0 or S and R is an aryl nucleus which carries a corboxyl group in ortho-posltion to the N=N group, which products form dark brown powders dyeing cotton light brown tints which are very fast to light.

5. As a new product the copper compound corresponding to the azodyestufi of the formula 

